Process for the conversion of heavy hydrocarbons into lighter hydrocarbons.



' W. A. HALL. PROCESS FOR THE CONVERSION OF HEAVY HYDROCARBONS INTO LIGHTER HYDROCARBONS. APPLICATION FILED JULY24 1914.

1,175,909. 'Patented 14, 1916.

o EXPANfiIOM CHAMBER CONDENSER PYROMETER 6A5 COLLETION VESSEL I FUEL PREHEATER L OIL STORAGE TANK WILLIAM A. HALL,

rnocnss FOR THE CONVERSION or HEAVY riwnnocnmaons INTO" LIGHTER HYDRO- an saa'rns PATENT. carton.

or NEW YORK, N. Y

cannons.

To all whom it may concern:

Be it known that I, WVILLIAM AUGUSTUS HALL, a citizen of the United States Hepublic, and resident of New York, N. Y., United States of America, have invented a certain new and useful Improvement in- Processes for the Conversion of Heavy I-Iydrocarbons Into. Lighter Hydrocarbons, of which the following is a specification.

' This invention relates to improvements in the hydrogenation of heavy hydrocarbons with the object of converting them into hydrocarbons of lower specific gravity and .boiling point "such as can be used successgen, or producer gas, or nascent hydrogen from the decomposition of water, the aflixation being usually accomplished by the well known catalytic action of nickel or other metal which will act in a similar manner, a process of this general character being claimed .in my copending application has presented diliiculties.

769,610, filed May 24:, 1913. These processes have been found very expensive as free by drogen is a costly material, and the N, GO and CO content of producer or water gas The improved process consists in subjecting .the volatilized heavy hydrocarbon, in the absence of steam or any extraneous source of hydrogen, either in the form of water, steam or added .hydrogen, to the action of heat and pressure in the presence of a catalyst capable of effecting the fixation of hydrogen to hydrocarbons, allowing the products to expand and thereby deposit carbon, and cooling the residual products to produce by condensation aliquid hydrocarbon containing less carbon than the said heavy hydrocarbon, and especially adapted for use in high speed internal combustion engines.

It has also been proposed to pass a mix: ture of 'oil and water or steam through tubes containing metallic nickel rods in a retort maintained at a dull red heat. My invention is distinguished from such a proc- Specification of Letters Patent. .Patented :Man 14, 1916.

' Application filed July 24, 1914. Serial -No.'852,965.

ess in that I pass the vaporized oil throughtubes containing rods of nickel or other hydrogenating catalyst, but with the addition thereto of no hydrogen, and no water or steam.

vIf the hydrocarbon oil isheated under a moderate pressure, say a pressure of about 5 atmospheres, to a temperature of upward of 600 C., in the presence of the catalyst, and in the absence of steam or any extraneous source of hydrogen, either'in the form of water, steam or added hydrogen gas, an efiicientconversion of the oil takes place, the oil being partially decomposed and gases set free, such gases being in turn decomposed by the heated catalyst with liberation of hydrogen which in a nascent state is to a considerable extent afiixed to the condensable portion of the decomposed hydrocarbon oil.

The catalysts I employ are substances such as the metals, or oxids of the metals, nickel, cobalt, silver,.palladium, chromium or manganese, which substances are hereinafter referred to under the term catalytic body of the nickel type.

Apparatus suitable for theperformance of the process is shown diagrammatically in the accompanying drawing.

heater A for raising the temperature of the before it enters the tubular converter B, so that the gas may be produced at asearly a sstage in the process as possible.

Theconverter shown is constituted by a serpentine inclined metallic tube so arranged that the circulation is through the top sec-' tion, then down and through the'next, and so on' to the bottom, the exposure being at first to the lowest temperature, which is at the" top, and gradually increasing toward the bottom. In the tubular elements of the converter is placed the catalytic material which rests in contact with the heated walls of the, tube. From the converter B the products are passed into an expansion cham- As shown, the apparatus includes, a pre-' ber C where their temperature is somewhat I I reduced. The said expansion chamber C may be provided "with a metallic gauze screen D, 'preferablv of conical shape, which will collect and extract any loose carbon that maybe set free (it being found that such carbon is most readily deposited at the point where expansion occurs and tothe greatest extent if the pressure'be' suddenly reduced from that in the converter (about,

atmospheres) down to atmospheric pres-' sure). This loose carbonis of course a productv of the decomposition. and its extraction from the heavy oil to a large extent accounts for the reduction ofthe specific gravity. I r

It is to be noted that the pressure of the vapors drops, materially, in passing from the converter B to the chamber l.' This drop in pressure appears to aid materially in the deposition of free carbon in large quantities in the receptacle C. By causing the carbonto deposit in the receptacle (J,

instead of in the elements of the converter B, there is no danger-of the converter being clogged up by means of this loose carbon.

It will be noted that the gases and vapors produced by the decomposition of the oil, will be caused to flow rather rapidly through the retort, and since the cross section of the space in the-retort is rather small, owing to the fact that the metal rod therein takes up quite a large part of the space therein, the current of gases and vapors flowing through the retort will carry along all the free carbon, or soot-like material, consequentlynot much of th-iswill deposit within the retort.

After the pressure falls, and the gases enter the largerchamber C, most all the free carbon will deposit in the expansion chamber the boilin v I it willfyie d from 50 to of a fue of a C, and on the gauze mem r D. Tarrymatters will likewise be separated in the chamber C. From the said expansion chamber O the products are passed through a-cooling specific gravity of about .765 with-a boiling point which is lower than that of commercial petrol. The product of-this process also contains a proportion of unsaturated hydrocarbons. The quantity of unsaturated hydrocarbons may vary more or less, but the quantity is always rather small, as compared with the products of some of the other processes with which I am yfamiliar." Of course it is not necessary to redistil the con- .densate, as thefractlonation can'be effected by a dephlegmator situated between the converter and the condenser.

Iflaving descrlbed myinventlon, I- declare atmospheric, thereafter allowingthe prodcatalyst capable of effecting therfixation of that what I claim and desire to secure by Letters Patent of-the United States is 1. The herein described method of convertingrelatively heavy liquid hydrocarbons into lighter and more volatile hydrocarbons,

which comprises the step of vaporizing said;

relatively heavy hydrocarbons, and causing a current of the vapors to flow, in the absence of extraneous hydrogen, and in the absence of free oxygen, in contact with a catalyst capable of effecting the fixation of hydrogen' to hydrocarbons, saidcatalyst being maintained at a temperature notr'naterially 1 below 300 C., and said7vap'ors being being maintainedunder pressure materially above ucts to expand into a separate expansion vessel, wherein the pressure 1s materlally lower, and the speed of the gases is materially lower, than in the vessel containing the catalyst, whereby the bulk of the free 5 carbon separates, and is deposited in said expansion vessel, and thereafter cooling the tion, a liquid hydrocarbon containing less carbon than said relatively heavy hydrocarbon and especially adapted for use in high speed internal combustlon engines.

'2. The herein described method of converting relatively heavy hydrocarbons into lighter and more volatile hydrocarbons,

suitable for use in internal combustion engines, which process comprises vaporizing said relatively heavy hydrocarbons. alone, causing the vapors thereby produced, in the absence of extraneous hydrogen, and in the absence of. free oxygen, to -flow' rapidly through a confined space under apressure residual products, to produce by condensaof several. atmospheres, at a temperature sufliciently'high to crack at least a portion of said hydrocarbon, in contact with a catalytic body, allowing the vapors so pro-' duced toexpandinto a separate expansion vessel, wherein the pressure is materially lower, than in the receptacle containing the catalytic body, and-wherein the .rate of flow of the vapors is lower than in the receptacle vessel, and thereafter cooling the vapors to condense liquid hydrocarbons.

3. The herein described method of converting relatively heavy liquid hydrocarbons into lighter and more volatile hydrocarbonsadapted for use'in high speed internalcombustion engines, consisting in vaporizing the relatively heavy hydrocarbons, and subjecting thevapors, under'pressure,in the absence of extraneous hydrogen, and in the absence of free oxygen, to the action of a containing the catalytic body, whereby free carbon will be deposited in said expansion hydrogen to hydrocarbons at a'temperature sufliciently high to cause the separation of free carbon, allowing the products to expand intoa separate expansion vessel, wherein a pressure is maintained, considerably lower than the pressure in the receptacle containing the catalyst, whereby the non-volatile materials are separated in said expansion vessel, and thereafter cooling the residual products, to produce by condensation, a liquid containing less carbon than the relatively heavy hydrocarbons employed.

' 4. In the treatment of hydrocarbons, of relatively high boiling points, for the production of hydrocarbons of lower boiling points, the step of passing a current of vaporized hydrocarbons, at a cracking temperature, and in the absence of extraneous hydrogen, in contact with a hydrogenating pressure of several atmos under pressure materially above atmospheric.

7. The herein described method of converting relatively heavy liquid hydrocarbons into lighter and more volatile hydrocarbons, which comprises the step of vaporizing said relatively heavy hydrocarbons, and causing a current of the vapors to flow, in the absence of extraneous hydrogen, and in the absence of free oxygen, in contact with a catalyst capable. of effecting the fixation of hydrogen to hydrocarbons, said catalyst being maintained at a temperature above about 600 0., and said vapors being maintained under pressure materially above atmospheric, thereafter allowing the products to expand into a separate expansion vessel, wherein the pressure is materially lower, and the speed of the gases is materially lower, than in the vesselcontai'm'ng the catalyst, passing the gases and vapors while at said lower pressure, through a device capable of removing free carbon, and thereafter cooling the residual products, to produce by condensation, a liquid hydrocarbon contain--. ing less carbon than said relatively heavy hydrocarbon and especially adapted for use in high speed internal combustion engines.

8. The herein described method of converting relatively heavy hydrocarbons into lighter and more volatile hydrocarbons,suitable for-use 1n internal-combustion engines.

'Wl1l0h process comprises vaporizing said relatively "heavy hydrocarbons alone, caus-' ing the vapors thereby produced, without the addition of other gases or vapors, to flow rapidly througha confined space under'superatmospheric pressure, and'at a temperature sufficiently high to cause the liberation of free carbon, while in contact With a catalytic body, allowing the vapors so produced to expand into a separate expansion vessel,

wherein the. pressure is materially. lower than in the receptacle containing the catalytic body, and wherein the rate of flow of the vapors is lower than in the receptacle containing-the catalytic body, and passing the gases and vapors through a separating medium.

9. In the production of motor fuel, the step of suddenly lowering the pressure of a flowing mixture containing gases and vapors and containing suspended particles of free carbon carried by said mixture, while causing said gases and vapors to enter an expansion vessel, wherein the speed of flow of the gases and vapors is materially decreased.

'10. A process of converti g heavy hydrocarbon oils into hydrocarb ns of lower boiling points which comprises passing the vapors of the hydrocarbons to be treated, un-

der pressure materially above atmospheric,

and in the absence of steam, over a substance capable of producing a catalytic action, while maintaining said substance at a temperature approximating a red heat.

11. A process of converting heavy petroleum oils into hydrocarbons of lower boiling points which comprises passing the vapors v of the hydrocarbons to be treated, under superatmospheric pressure and in the absence of steam, over a hydrogenating catalyst while maintaining said catalyst at a temperature approximating a red heat.

12. A process of converting heavy hydrodescribed improvement which comprises passing such oil, in the form-of a flowing 1 current, in the substantial absence of extraneous water, through a coil maintained at a temperature not materially below 500 C., while at a pressure sufiiciently low to allow vaporization,- but materially above atmospheric, and thereafter rapidlylowering the pressure of the flowing mixture containing gases and vapors and containing suspended particles of free carbon carried by said mixture, and causing said gases and vapors to enteran expansion vessel, whereinthe speed of flowof the gases and vapors is materially decreased.

14. A process ofconverting heavy hydrocarbon oils into hydrocarbons of lower boilcarbon oils into hydrocarbon oils having 1 than those of ordinary -gasolene, the herein ing points which comprises passing the va pors of the h drocarbons to be'treated, vunder a pressure several atmospheres, in the ab- .sence of steam, over a metalhc substance capable of producing a catalytic action, while Qmaintainmg. said substance at atemperature capableof cracking the heavy oils.

15. A process of converting lamp oils or other hydrocarbons into hydrocarbons of i lower boiling points, which comprises passing the va ors of the hydrocarbons to be treated, 'un er a pressureof several atmospheres', over 'a catalytic metal maintained at a temperat re at which said catalytic metal possesses catalytic activity.

16. -A process of converting heavy hydrocarbons ln'to hydrocarbons of lower boiling points which comprises passing the vapors of said hydrocarbons, under superatmospheric pressure and in the absence of steam or added hydrogen over a substancecapable of producing a catalytic action, while maintained at a temperature capable of cracking oils. 7

17. A process of convertin heavy hydrocarbons mtohydrocarbons ,0 lower boiling points, which comprises passing the vapors of steam or other extraneous hydrogen, under superatmospheric pressure, over a catature approkimating a red heat,vallowing the ref heavy hydrocarbons-in the'absence products of the reaction 'to expand to. a lower pressure, and removing the solid materials from the vaporous products.

18. 'In thev manufacture of motor fuel.

Q from hydrocarbon oils of which at least portions have boiling points materially higher than those of ordinary gasolene, the step of passing such an oil in the form of a flowing current, in the substantial absence of extraneous Water, through a coil maintained at -a temperature not materially below 500 0.,

while at a pressure sufiiciently low to allow ,vaporization, but materially above atmospheric. 4 v

In testimony whereof I have signed my name to this specification in the presence'gf two subscribing witnesses.

. 30 lytic body of the nickel type, at a .tempera- 

